Oil recovery and environmental cleanup compositions

ABSTRACT

This invention relates to improvements in products and processes for cleaning up oil, chemical, or other hydrocarbon spills, and cleaning up the environment where such spills have occurred. In one aspect of the invention, there is provided an adsorbent polymeric composition which is oleophilic and capable of adsorption of other chemicals and hydrocarbons from both land and water, the adsorbent composition including polyethylene/vinyl acetate copolymer, catalyst, cross-linking agent, lubricant, blowing agent and a bulking agent. In a second aspect of the invention there is provided a method of manufacture of an adsorbent composition for use in retrieving and recycling oil, chemicals and hydrocarbons from land or water environments.

FIELD OF THE INVENTION

This invention relates to improvements in products and processes forcleaning up oil, chemical, or other hydrocarbon spills, and cleaning upthe environment where such spills have occurred.

BACKGROUND

When an oil, chemical, or other hydrocarbon spill occurs in water aneffort is made to absorb the oil, chemical, or other hydrocarbon andrecover or retrieve it. This is done with the use of straw, hay,sawdust, absorbent pads or booms, “Kitty Litter” and several otheradsorbents. However these adsorbents hold water as well as the oil. Theytherefore become saturated with a mixture of water and oil, chemical, orother hydrocarbon and sink. Generally speaking, only a small portion ofthe spilt oil, chemical, or other hydrocarbon is removed from theenvironment and recovered for further processing. The remainder of theoil, chemical, or other hydrocarbon spill is burnt, dispersed or treatedwith harsh chemicals, which themselves often cause further environmentaldamage. Much of the oil, chemical, or other hydrocarbon is trapped inthe sunken adsorbent and may be slowly released into the water over aperiod of many years causing long-term environmental damage.

When an oil, chemical, or other hydrocarbon spill occurs on land asimilar process using adsorbent booms or embankments is used but anyexcess which is not readily collected or retrieved is frequently washedaway with water and/or detergents into the nearest drain, or burnt, ordispersed over a wide area.

One example of an environmentally sympathetic product used in theretrieval of oil, chemicals or other hydrocarbons from the environmentis, for example, a product made from recycled waste plant fibres whichare hydrophobic and oleophilic.

Other environmentally unsympathetic solutions for oil spills, forexample, include the use of surfactants and dispersion agents.

The need for better recovery products and processes has been recognisedworldwide. To date there has been no suitable product that will collectthe oil, chemical, or other hydrocarbon, hold it in suspension, andcause it to separate from the water or soil so that it can be recoveredor retrieved. It is an object of this invention to provide recoveryproducts and processes suited to the efficient removal of oil, chemicalor other hydrocarbon spills from a polluted environment.

SUMMARY OF THE INVENTION

In one aspect of the invention, there is provided an adsorbent polymericcomposition which is oleophilic and capable of adsorption of otherchemicals and hydrocarbons from both land and water, the adsorbentcomposition including polyethylene/vinyl acetate copolymer, catalyst,cross-linking agent, lubricant, blowing agent and a bulking agent.

One advantage of the composition according to the invention is that itis biodegradable and will be broken down by the action of ultravioletlight such as the ultraviolet rays of the sun. The final products ofthis biodegradation process are environmentally friendly and suitablefor marine and/or land use.

In a preferred embodiment of this aspect of the invention, the adsorbentcomposition additionally includes one or more of anti microbial andantifungal agents, odour-masking agents, wetting agents and othersuitable additives such as, for example, colouring agents and/or dyes.

A suitable catalyst is any substance or chemical that is capable ofstarting or kicking the cross linking of the polymeric compositionduring preparation and may be, for example, one or more of zincstearate, lead, chromium, copper, cobalt, nickel, silica or zinc oxideor compounds and ionic forms thereof. Zinc oxide is preferred.

Preferably the zinc oxide is present in amounts of 0.2-2% w/w.

Preferably the polyethylene/vinyl acetate copolymer is made up ofbetween about 2-30% vinyl acetate and is present in amounts of about75-95% w/w. Preferably the vinyl acetate is ethyl vinyl acetate. Theproportion of ethyl vinyl acetate present may be varied so as to easethe handling of the product according to the invention.

The melt flow index of suitable polyethylene/vinylacetate copolymers maybe varied according to need, and according to the mode and manner ofapplication. Preferably, the melt flow index of the copolymer is 0.2-600g/10 min.

One suitable polyethylene/vinylacetate copolymer is Escorene™ LDPEavailable from a variety of sources.

A suitable cross linking agent is any substance or chemical that iscapable of linking a cellular structure together and may be, forexample, one or more diacyl peroxide, dialkyl peroxide, ketone peroxide,peroxydicarbonates, peroxyesters, tertiary alkyl hydra peroxides,tertiary amyl peroxides, acid chlorides, hydrogen peroxides whether theybe organic or inorganic or dicumyl peroxide.

The cross linking agent is preferably peroxide, and more preferably,dicumyl peroxide. The peroxide is preferably used as a 99% solution butmay be as low as a 20% solution. It is present in amounts of about0.2-1.8% w/w.

One preferred lubricant according to the invention is a fatty acid,preferably stearic acid, but it will be appreciated, for example, thatother fatty acids such as palmitic acid may be suited to the process.The lubricant may be present in amounts of about 0.5-1.75% w/w.

A suitable blowing agent may be any substance which alone or incombination with other substances is capable of producing a cellularstructure in the adsorbent composition and is preferably present inamounts of about 1-7% w/w. Blowing agents include compressed gases thatexpand when pressure is released, soluble solids that leave pores whenleached out, liquids that develop cells when they change to gases, andchemical agents that decompose or react under the influence of heat toform a gas. Chemical blowing agents range from simple salts such asammonium or sodium bicarbonate to complex nitrogen releasing agents. Apreferred blowing agent is azodicarbonamide.

Suitable bulking agents may include one or more of calcium carbonate,talc or any other substitute for these substances and may be present inamounts of about up to 25% w/w.

Suitable odour masking agents may include, for example, one or more ofti-tree oil, lavender oil and like substances and can be present inamounts of about up to 1% w/w. These substances, for example ti-treeoil, may also act as anti fungal and anti microbial agents.

Wetting agents may be useful in the manufacturing process to preventdust generation and might be present in amounts of about up to 29% w/w.Suitable wetting agents may include, for example, white oil. Thissubstance, for example, may have a secondary function as, for example,an insecticide.

In a second aspect of the invention there is provided a method ofmanufacture of an adsorbent composition for use in retrieving andrecycling oil, chemicals and hydrocarbons from land or waterenvironments, the method including the steps of forming an admixture forexample, preferably in the form of a crepe of the components of theadsorbent composition of this invention, subjecting said admixture topressure and optionally, temperature and forming the resultant cake intoa shape or form suited to the environment of application of thecomposition.

Preferably, the admixture is treated at a temperature of between 70-400°C. and at pressure of about 12000 tonne/m². The duration of saidtreatment will vary according to the volume of adsorbent-compositionbeing produced and the surface area of the vessel in which the treatmentis occurring.

The adsorbent composition may be granulated after the heat and pressuretreatment, but this granulation may also take place during the heat andpressure treatment, for example, by use of injection moulding equipmentwhich forces the formation of a particularised product. Alternatively,the product may be shaped so as to form a sweep, boom or case as needsbe. The adsorbent composition may also be applied in a liquid form inwhich case it will be necessary to add a co-solvent to the system tosolubilise the composition. This form of the adsorbent composition isespecially useful in environments where high wind is a factor.

In a third aspect of the invention the adsorbent composition preparedaccording to the method described hereinabove, having thecharacteristics described may be incorporated into a product such as afilter for off-site treatment of contaminated water or soil. In thisaspect, the polluted water or soil could be removed by any suitablecollection means and transported to said filter for treatment. Thefilter could then be treated for recovery of the pollutant and adsorbentcomposition, or the gelatinous mass arising from the treatment removedfrom the filter and treated independently of any filter structure.

In a fourth aspect of the invention, there is provided a method oftreating an environment to remove an oil, chemical or other hydrocarbonpollutant including applying to said environment an adsorbentcomposition according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

When the composition according to the invention, being an inertadsorbent, comes into contact with oil, chemical, or other hydrocarbon,it collects, and forms a gelatinous mass with, the oil, chemical, orother hydrocarbon without any chemical reaction taking place between thecomposition according to the invention and the oil, chemical, or otherhydrocarbon. This allows the process to be easily reversed so that thegelatinous mass may be separated into adsorbent composition and the oil,chemical, or other hydrocarbon without the oil, chemical, or otherhydrocarbon being affected by its contact with the adsorbent compositionaccording to the invention.

When an oil, chemical, or other hydrocarbon spill occurs on water theoil, chemical, or other hydrocarbon tends to float for some time. Thecomposition according to the invention after application by spreading orspraying on to the spill, will collect the oil, chemical, or otherhydrocarbon suspended in or on water and hold it in suspension in theform of a gelatinous mass constituted by the oil, chemical or otherhydrocarbon impregnated adsorbent. This gelatinous mass will notappreciably absorb water and hence in the instance where it is used totreat chemical or oil spills in or on water, will continue to float sothat it can be recovered or retrieved. Surfactant may be used to atleast partially fluidise the adsorbent composition to assist inspreading or spraying. The recovered or retrieved mass is then treatedso as to desorb the oil, chemical, or other hydrocarbon for furthertreatment or processing. The adsorbent according to the invention maythen be cleaned for further use.

The floating mass is easily recognised and can be recovered or retrievedby normal means including, but not limited to, suction, scoop, filter,or water-porous conveyor belt or is simply floated or scraped off thewater. The oil, chemical, or other hydrocarbon may be recovered by meansof compression, suction, centrifugal force, or any other suitable typeof filter which will not be detrimentally affected by the compositionitself, the oil, chemical, or any other hydrocarbon, the water or acombination of the oil, chemical, or other hydrocarbon and the water atthe operating temperature and environmental conditions.

When an oil, chemical, or other hydrocarbon spill occurs on land theoil, chemical, or other hydrocarbon may remain on the surface for atime, or penetrate into the surface layer at a rate determined by thetype of soil or substrate and by the type of oil, chemical, or otherhydrocarbon in the spill. Chemical reactions between the contents of thespill and the soil or substrate will also affect the rate ofpenetration.

In a similar fashion to the mechanism of treatment and retrieval of oil,chemical and hydrocarbons from water, on land, after application byspraying or spreading, the adsorbent will adsorb the pollutant oil,chemical or hydrocarbon waste and hold it in the form of a gelatinousmass. This mass may then be recovered or retrieved by suitablemechanical means of a scoop, suction or by other suitable means orwashing it into a recovery or retrieval point with the use of availablewater and treated so as to desorb by compression, suction, centrifugalsystem, or any other type of suitable filter, the oil, chemical orhydrocarbon pollutant for further treatment or processing.

The filter removes the collected oil, chemical, or other hydrocarbon outof the gelatinous mass and recovers or retrieves it for storage,transport or further processing. The composition according to theinvention, being substantially, if not totally, cleaned in the filterprocess, can be immediately returned to the oil, chemical, or otherhydrocarbon spill and reused for a number of cycles.

In an embodiment in which the oil, chemical, or other hydrocarbon hasleached, or penetrated, or soaked into the soil or environment, cleaningand retrieval is commenced by removing the contaminated soil from itsnatural or initial location into a water-filled container or bath thusallowing the oil, chemical, or other hydrocarbon to be released into thewater. It may be necessary to adjust the temperature of the mixture inthe bath and/or cause some agitation of the mixture or use other methodsto enhance the release of the oil, chemical, or other hydrocarbon fromthe soil into the water.

The mixture is then treated as a water-based spill of oil, chemical, orother hydrocarbon by spraying or spreading the adsorbent compositionaccording to the invention onto the mixture by any suitable means andallowing it to collect the oil, chemical, or other hydrocarbon. Theresultant gelatinous mass is recovered or retrieved by means of a scoop,suction, floatation, or other suitable means and fed into a compression,suction, or centrifugal, or other type of suitable filter. The filterremoves the collected oil, chemical, or other hydrocarbon out of thegelatinous mass and recovers or retrieves it for storage, transport orfurther processing. The composition according to the invention, beingsubstantially, if not totally, cleaned in the filter process, can beimmediately returned to the bath and reused for a number of cycles. Whenthe oil, chemical, or other hydrocarbon has been removed from the bath,the soil can then be removed from the water and soil mixture by anysuitable means and dried so that it can be returned to its originallocation or to an alternate site.

In the event that a small amount of the adsorbent composition accordingto the invention inadvertently remains in the environment as a result ofnot being completely recovered or retrieved, the adsorbent compositionwill be degraded by the ultraviolet light of the sun so that nolong-term harm will be done to the environment.

In a preferred embodiment the composition according to the invention maybe made by admixing suitable proportions of calcium carbonate, ethylvinyl acetate, stearic acid, blowing agent, white oil, ti-tree oil,lavender oil, dicumyl peroxide, and zinc oxide in a roller mill, andthen subjecting the mixture to a temperature between 70-400° C. andpressure of between approximately one thousand (1,000) and twelvethousand (12,000) tonne per square metre in a seated vessel to allow thechemicals to react to form a polymeric solid of suitable particle size.

The step of admixing the components of the composition is exothermic.When a polyethylene/vinylacetate of low MFI is used e.g. about 2 g/10min, a temperature of about 70-160° C. is desirably maintained in theroller mill. When copolymers of higher MFI are used e.g. 30-600 g/10min, cold milling is required and it will not be necessary to performthe admixing step at elevated temperature.

During the manufacturing process, other additives may be added accordingto need and the conditions of the manufacturing process can be alteredto enhance the properties of the product or to alter the properties tomake the product suitable for other applications. The product may thenbe granulated by known means if necessary and is subsequently packaged.

In its natural form the composition according to the invention comes inthe form of white powder or granule. It may-be possible to colour thecomposition, but care needs to be taken in the development of acolouring agent so that the basic chemical, physical and electricalproperties of the composition according to the invention are notadversely affected. Colouring may be used to identify different gradesor particle sizes of the product for use in different environments orfor different types of spill.

One preferred composition according to the invention is as follows:Component kg polyethylene/ethyl vinyl acetate (18%) 25.00 [MFI-2 g/10mins] Azodicarbonamide 0.89 Dicumyl peroxide 0.18 Stearic Acid 0.20 ZincOxide 0.240 Calcium carbonate 3.570

This may be scaled up according to need.

EXAMPLES 1-11

Other examples of composition according to the invention are as follows:Amount (g) FUNCTION COMPONENT 1 2 3 4 5 6 7 8 9 10 11 blowingAzodicarbonamide 778 700 530 488 800 773 758 700 443 907 890 agent (AC2)catalyst Zinc oxide 195 240 198 156 206 198 226 180 156 188 240lubricant Stearic acid 150 150 150 150 150 150 150 150 150 150 200 cross(X/L 99%) 118 118 106 148 116 106 112 118 148 115 180 linker dicumylperoxide bulking Calcium 2248 2100 2248 2248 2248 2248 2248 2248 22482248 3570 agent carbonate copolymer EVA FL 00206 — 16000 — 16000 — — —16000 — — EVA FL 00209 — 16000 — 16000 — — — — — 16000 EVA FL 00212-21816000 — 16000 16000 — 16000 16000 — — — 25000 EVA VL 00328 — — — — 16000— — — 16000 16000 colourant 200 200 75 200 200 200 200 200 200 200

The composition according to the invention has been tested withcontrolled spills on a number of oil, chemical, or other hydrocarbonbased products and is found to be able to collect oil, chemical, orother hydrocarbon products ranging from, but not limited to, crude oilthrough refined oils and fuels to paraffins, waxes, animal and vegetableoils and other hydrocarbons.

EXAMPLE 12

In a test conducted by The Murray-Darling Freshwater Research Centre, ofNew South Wales, Australia, to ascertain the rate of recovery of oilfrom a contaminated water sample, the following procedure was conducted.

200 ml of distilled water was weighed into a beaker and 20 ml of oil(unspecified) was added. In 1 g increments, a sorbent compositionaccording to example 11 was added until saturation occurred or until thedesired result was achieved. The water with oil and product added wasstirred to stimulate a wave action. The sorbent product/oil compositewas removed with a filter scoop and weighed. The weight of the remainingwater was recorded. The oil in the product sample was then analysedusing gravimetric method APHA5520B.

The following results were achieved: Sample A B C oil/grease mg/l 7.513.0 9.0 Petroleum hydrocarbon mg/l 1.0 6.0 2.0

EXAMPLES 13-16

The following tests were conducted by the Industrial Research Instituteof Beirut, Lebanon to test the ability of a sorbent compositionaccording to example 11 to adsorb oils and other hydrocarbons spilled insand, stones and water.

EXAMPLE 13 Contaminated Sand and Rocks

Two kilograms of mixed sand and stones contaminated with fuel oil weremixed with 100 g of the sorbent material for 15 minutes. Water at 35° C.(2.5 litres) was added and mixed for another 15 minutes. Floatingmaterial was skimmed with a sieve. Sand mixture, remaining water and theskimmed material (weighed 321 g on air dried basis) were tested for oiland grease content. Remaining water was also tested for BiochemicalOxygen Demand (BOD₅).

The results were found as follows: Skimmed material Sand mixture Water(on air dried basis) Oil and grease 7.70 g/kg <0.1 mg/l <0.1 mg/l(before treatment) Oil and grease 291 mg/kg 3 mg/l 20 g/kg (aftertreatment) BOD₅ as O 18 mg/l

EXAMPLE 14 Sand Mixture Containing 200 q/kg of Fuel Oil

A 400 g sample of “clean” sand and stones mixture was mixed with 100 gof fuel oil and 20 g of the sorbent material.

Water at 35° C. (200 ml) was added and mixed for 15 minutes.

Floating material was skimmed with a sieve (weighed 155 g on air driedbasis). Samples were tested and results were found as follows: Skimmedmaterial Sand mixture Water (on air dried basis) Oil and grease 200 g/kg<0.1 mg/l — (before treatment) Oil and grease 3.5 g/kg 54 mg/l 303.6g/kg (after treatment)

EXAMPLE 15 Sea Water Containing 200 g/l Fuel Oil

400 g of fuel oil were mixed with 1.5 litres of sea water.

100 g of the sorbent material was added and mixed for 15 minutes.

Floating material was skimmed with a sieve (weighed 485 g on air driedbasis). Water and the recovered floating material were tested for oiland grease. Water was also tested for Biochemical Oxygen Demand (BOD₅).Skimmed material Water (on air dried basis) Oil and grease 200 g/l(before treatment) Oil and grease 23 mg/l 276 g/kg (after treatment)BOD₅ as O 19.5 mg/l —

EXAMPLE 16 Sand Containing 380 g/kg Fuel Oil

400 g of sand and stones were mixed with 250 g of fuel oil. 35 g of thesorbent material were added along with 1 litre of water. Floatingmaterial was skimmed with a sieve (weighed 450 g on air dried basis).Tests were performed as described in Ex.13. Skimmed material Sandmixture Water (on air dried basis) Oil and grease 385 g/kg <0.1 mg/l<0.1 mg/kg (before treatment) Oil and grease 58 g/kg 725 mg/l 413 g/kg(after treatment)

EXAMPLE 17

The following trial on a sorbent composition according to example 11 wasconducted by Science Applications International Corporation (SAICCanada).

The purpose of these tests was to evaluate the sorbent's performance asper the Environment Canada Sorbent Performance Test Program, using ASTMStandard Method of Testing Sorbent Performance of Adsorbents (F726-99).This protocol is based, in part, upon test methods listed in theCanadian General Standards Board Method for Testing Sorbents(CAN/CGSB-183.24), and internal standards initially developed in part bythe Emergencies Engineering Technologies Office (formerly theEmergencies Engineering Division) of Environment Canada.

Procedures

Materials and Equipment

Sorbent Description

The following brief description of the sorbent is based on informationsupplied by the manufacturer and from the quantitative and qualitativeobservations obtained during testing. Such information is provided sinceit may be useful when interpreting or comparing results.

The sorbent supplied for testing is described as a granular(non-metallic) material. Two samples of the sorbent particulate werereceived, one fully white and the other with a coloured fleck (indicatedas being for safety reasons—made for defence and government departmentsonly). The coloured fleck sample was used for testing purposes—having ameasured density of approximately 0.090 g/cm 3.

Test Liquids

The following test liquids were used: Density Viscosity Temperature TestLiquid (g/cm 3) (cP) (° C.) Diesel 0.829 3 20 Light Crude Oil 0.944 29020 Heavy Crude Oil 0.995 2050 20Equipment

The following apparatus was used to measure physical and chemicalproperties of the sorbent and/or test liquids. Density Anton-Paar DMA 35hand-held digital densitometer. The unit contains a borosilicateU-shaped oscillating tube and a system for electronic excitation,frequency counting and display. An injected sample volume is keptconstant and is vibrated. The density is calculated based on ameasurement of the sample oscillation period and temperature. Replicatemeasurements are conducted and the average density is reported.Viscosity Brookfield DVII+ viscometer powered by a precision motor andequipped with a beryllium copper spring to measure torque. The degree towhich the spring is wound is proportional to the viscosity of the fluid.Several of the following spindles are used per measurement whenpossible: LVT spindles (#1, #2, #3, #4),. Ultra Low viscosity Adapter(ULA) and spindle, Small Sample Adapter (SSA) and spindles SC4-18,SC4-31. Models are stated to be accurate to within 1% of their fullscale range when employed in the specified manner. Readings should bereproducible to within 0.2% of full scale subject to environ- mentalconditions such as variation in fluid temperature. Calibrations areconducted with Brookfield Standard Fluids. Mass Sample mass is measuredusing a Mettler PM 4000 analytical balance. The scale resolution is 0.01g and the reported reproducibility is 0.01 g. Test Cells: Pyrex 190 mm(diameter) × 100 mm (depth) crystallizing dishes are the typical testcells used although other vessels can be used in order to accommodatespecial materials Weighing Pans Non-stick coated pans of 20 cm diameter.Mesh Basket Mesh baskets (mesh size approximately 1.1 mm diameter) areused to contain and drain Type II (particulate) samples. Shaker Table AnEberbach Corporation shaker table, modified to hold three 4L jars isused to agitate samples. The table is set at a frequency of 150 cyclesper minute with an amplitude of 3 cm.Test Protocol

The following summary test protocol which is applicable to Type II(particulate) sorbents was utilized.

The Dynamic Degradation Test

This procedure is designed to determine the buoyancy, hydrophobic andoleophilic properties of a sorbent sample under dynamic conditions. Asorbent sample is placed in a sealed 4 L jar which is half-filled withwater. The jar is placed on its side and mounted on a shaker table, setat a frequency of 150 cycles per minute at an amplitude of 3 cm, for aduration of 15 minutes. The contents of the jar are allowed to settlefor a period of 2 minutes, after which observations pertaining to thecondition of the water and the sorbent sample are recorded. If greaterthan 10% of the sorbent is observed to sink or the water column isrendered contaminated with sorbent particles, then the sorbent isdesignated with a Failure and is not recommended for use on open water.The sorbent samples are removed from the jar and the water pick-up ratiois determined.

3 mL of oil is added to the surface of the test jars which have beenhalf-filled with water. The wetted sorbent samples used in the beginningof this procedure are returned to the jar and the container is placed onits side and mounted on the shaker table for an additional 15 minutes.The contents of the jar are allowed to settle for a period of 2 minutesand observations pertaining to the existence of any oil sheen on thesurface of the water is noted.

The Oil Adsorption—Short Test (15 Minutes)

This procedure is designed to determine a sorbent's pick-up ratio whenplaced in a pure test liquid under stagnant conditions. The sorbentsample is initially weighed and the value recorded. A test cell isfilled with a layer of test liquid to a depth of approximately 80 mm.The sorbent sample is placed in a fine mesh basket and lowered into thetest cell. After 15 minutes, the sorbent is removed from the cell andallowed to drain for 30 seconds (sorbents tested in Heavy Oil aredrained for 2 minutes). The sorbent is then transferred to a weighingpan and the weight recorded. All tests are conducted in triplicate.

The Oil Adsorption—Long Test (24 Hours)

This procedure is designed to determine a sorbent's pick-up ratio whenplaced in a pure test liquid under stagnant conditions. The sorbentsample is initially weighed and the value recorded. A test cell isfilled with a layer of test liquid to a depth of approximately 80 mm.The sorbent sample is placed in a fine mesh basket and lowered into thetest cell. After 24 hours, the sorbent is removed from the cell andallowed to drain for 30 seconds (sorbents tested in Heavy Oil aredrained for 2 minutes). The sorbent is then transferred to a weighingpan and the weight recorded. All tests are conducted in triplicate.

Results and Discussion

Test results are as follows:

The Dynamic Degradation Test

After shaking for 15 minutes and settling for 2 minutes, the bulk of thesorbent material was observed to be floating on the water column. Thebulk water remained clear, with little evidence of clouding or colourchange.

After shaking for 15 minutes following the addition of 3 mL of oil,there was little evidence of clouding in the water column, however,trace amounts of oil sheen remained on the water surface. Due to thesefactors the sorbent was deemed to have passed this test and is thereforerecommended for use on waterways and for land applications. DYNAMIC:DEGRADATION PRE-TEST 1 2 3 Temperature (° C.) 21 21 21 Sample weight (g)6.13 6.19 6.50 Weight of wetted sorbent (g) 33.66 35.74 21.61 Initialwater pickup ratio 4.5 4.8 2.3 (g liquid/g sorbent) Average liquidup-take 3.9 (g liquid/g sorbent) Standard Deviation 34.7% (g liquid/gsorbent) Buoyancy test (Pass/Fail) PassComments:

-   sorbent floats

lost a significant amount of sorbent through filter. DYNAMIC:DEGRADATION TEST 1 2 3 Temperature (° C.) 23 21 19 Sample weight (g) Asabove Persistence of oil sheen Yes Yes Yes on surface (Yes/No)Comments

-   sorbent floats freely 1 water remains clear-   VERY SMALL oil sheen remains on surface: stirred containers after 2    minutes and sheen got smaller    List of Possible Comments:-   Sorbent: floats freely, 25%150%/75% submerged; sorbent still    floating, sinks, dissolves.-   Water: remains clear, becomes slightly coloured, becomes cloudy,    becomes murky.

Oil: sheen remains on surface, no sheen on surface. Density ViscosityTemperature COMMENTS Oil Used (g/cm³) (cP) (° C.) Medium 0.944 290 20(Crude oil)The Oil Adsorption—Short Test

Following completion of the above test, new sorbent samples were exposedto a range of test oils. Based on 15 minute exposure and 0.5 or 2 minutedrain periods, the sorbent was observed to have the following oilsorption ratios: Oil Viscosity Pick-up ratio Oil Type (cP) (g oil/gsorbent) Diesel fuel 3 7.0 Medium oil 290 10.7 Heavy Oil 2050 5.2

The Short L-Test (15 minutes) is the designated test which indicatesstandard performance.

Short L Test—15 minutes Liquid #1 Liquid #2 Liquid #3 Sample SampleSample 1 2 3 1 2 3 1 2 3 Temperature (° C.) 19 19 19 19 19 19 19 19 19Sample weight (g) 5.63 5.71 5.61 6.10 6.07 6.43 4.87 5.99 4.81 Wetsample weight (g) 40.99 47.05 48.06 70.14 72.12 74.69 34.21 33.17 28.67Initial Sorption Capacity 6.28 7.24 7.57 10.50 10.88 10.62 6.02 4.544.96 (g liquid/g sorbent Average liquid up-take 7.0 10.7 5.2 (g liquid/gsorbent) Standard Deviation  9.5%  1.8% 14.8% (g liquid/g sorbent)

Density Viscosity Temperature Liquid Used (g/cm³) (cP) (° C.) CommentsLight (Diesel) 0.829 3 20 Float Medium 0.944 290 20 Sorbent floats(crude oil) Heavy 0.995 2050 20 Floats, not (crude/bunker) fullysaturated

Adsorption—Long Test Oil Viscosity Pick-up ratio Oil Type (cP) (g oil/gsorbent) Diesel fuel 3 5.8 Medium oil 290 12.0 Heavy Oil 2050 13.2

Long L Test—15 minutes Liquid #1 Liquid #2 Liquid #3 Sample SampleSample 1 2 3 1 2 3 1 2 3 Temperature (° C.) 19 19 19 19 19 19 19 19 19Sample weight (g) 5.14 5.34 5.29 5.76 5.58 7.24 7.42 7.62 6.30 Wetsample weight (g) 33.22 36.30 38.48 71.43 75.28 95.50 104.71 107.3791.41 Initial Sorption Capacity 5.46 5.80 6.27 11.40 12.49 12.19 13.1113.09 13.51 (g liquid/g sorbent Average liquid up-take 5.8 12.0 13.2 (gliquid/g sorbent) Standard Deviation  7.0%  4.7%  1.8% (g liquid/gsorbent)

Density Viscosity Temperature Liquid Used (g/cm³) (cP) (° C.) CommentsLight (Diesel) 0.829 3 20 Float Medium 0.944 290 20 Float/sorbent out(crude oil) mostly in one chunk Heavy 0.995 2050 20 Float (crude/bunker)

Conclusions

The sorbent material was tested using ASTM F726-99 Protocol in order toevaluate its performance. It passed the buoyancy test by having lessthan 10% of the product sink under dynamic (wave) conditions.

The sorbent appeared to have reached saturation in all tests except theShort Test in Heavy Oil. This was confirmed by the results of the LongTest, which showed higher values (over 50% higher pick-up ratio whencompared to Short Test). There was variability in the testing resultswhich forced repeat testing to be undertaken. Due to the relatively fineparticle size of the sorbent it is thought that losses through the testbaskets contributed greatly to this variability.

The oil sorption capacities, expressed as weight ratios of liquid sorbedper unit weight of sorbent, varied between 5.2 and 10.7 for the standard15 minute tests.

It will be evident that the composition according to the invention isuniquely able to be re-used thereby reducing the cost of processingmaterials, the cost of processing and disposal of waste, and the cost oftransport and storage. Moreover the adsorbent composition presents areduced risk to personnel because it is biodegradable and non-toxic.

The advantages of the process of the invention include, but are notlimited to, the use of only non-toxic and biodegradable materials, theability of the process to return uncontaminated oil, chemical, or otherhydrocarbon to the original source of the spill or back to the refinery,and the re-usability of the composition according to the invention afterseparating it from the oil, chemical, or other hydrocarbon at the siteof the spill.

It will be appreciated that the invention goes beyond the scope of thelimited disclosure outlined herein above, and that nothing stated hereinabove should be taken to unnecessarily limit the scope of the inventionclaimed.

1. An adsorbent polymeric composition which is oleophilic and capable ofadsorption of chemicals and hydrocarbons from land and water, theadsorbent composition including polyethylene/vinyl acetate copolymer,catalyst, cross linking agent, lubricant, blowing agent and bulkingagent.
 2. An adsorbent polymeric composition according to claim 1wherein said polyethylene/vinyl acetate copolymer is apolyethylene/ethyl vinyl acetate copolymer.
 3. An adsorbent polymericcomposition as claimed in claim 1 wherein said polyethylene/vinylacetate copolymer is present in the composition in an amount of 75-95%w/w.
 4. An adsorbent polymeric composition as claimed in claim 1 whereinsaid polyethylene/vinyl acetate polymer is made up of 2-30% w/w vinylacetate.
 5. An adsorbent polymeric composition as claimed in claim 1wherein said catalyst is selected from the group consisting of one ormore of zinc oxide, zinc stearate, lead, chromium, copper, cobalt,nickel, silica, compounds or ionic forms thereof and is present inamounts of 0.2-2.0% w/w.
 6. An adsorbent polymeric composition asclaimed in claim 1 wherein said crosslinking agent is selected from thegroup consisting of one or more of diacyl peroxide, dialkyl peroxide,ketone peroxide, peroxy dicarbonates, peroxy esters, tertiary alkylhydroperoxides, tertiary amyl peroxides, acid chlorides or hydrogenperoxides and is present in amounts of 0.2-1.8% w/w.
 7. An adsorbentpolymeric composition as claimed in claim 1 any one of claims 16 whereinthe bulking agent is selected from the group consisting of calciumcarbonate or talc and is present in amounts of up to 25% w/w.
 8. Anadsorbent polymeric composition as claimed in claim 1 wherein thelubricant is a fatty acid, preferably stearic acid.
 9. An adsorbentpolymeric composition as claimed in claim 1 further including one ormore of odour masking agents, antimicrobial agents, antifingal agents,wetting agents, colourants or dyes.
 10. An adsorbent polymericcomposition as claimed in claim 1 including polyethylene/ethyl vinylacetate, blowing agent, dicumyl peroxide, stearic acid, zinc oxide andcalcium carbonate. 11-13. (canceled)
 14. A method of manufacture of anadsorbent polymeric composition for use in retrieving and recyclingoils, chemicals or hydrocarbons from land or water environmentincluding: forming an admixture of polyethylene/vinyl acetate copolymer,catalyst, cross linking agent, lubricant, blowing agent and bulkingagent; subjecting said admixture to pressure of about 12000 tonne/m²;and forming the resultant cake into a shape or form suited to theenvironment to be treated.
 15. A method according to claim 14 whereinthe adsorbent polymeric composition is oleophilic.
 16. A method asclaimed in claim 14 wherein subjecting said admixture to pressure ofabout 12000 tonne/m² further includes subjecting said admixture to atemperature in the range of 70-400° C.
 17. A method as claimed in claim14 wherein said polyethylene/vinyl acetate copolymer is apolyethylene/ethyl vinyl acetate copolymer.
 18. A method as claimed inclaim 14 wherein said polyethylene/vinyl acetate copolymer is present inthe composition in an amount of 75-95% w/w.
 19. A method as claimed inclaim 14 wherein said polyethylene/vinyl acetate polymer is made up of2-30% w/w vinyl acetate.
 20. A method as claimed in claim 14 whereinsaid catalyst is selected from the group consisting of one or more ofzinc oxide, zinc stearate, lead, chromium, copper, cobalt, nickel,silica, compounds or ionic forms thereof and is present in amounts of0.2-2.0% w/w.
 21. A method as claimed in claim 14 wherein saidcrosslinking agent is selected from the group consisting of one or moreof diacyl peroxide, dialkyl peroxide, ketone peroxide, peroxydicarbonates, peroxy esters, tertiary alkyl hydroperoxides, tertiaryamyl peroxides, acid chlorides or hydrogen peroxides and is present inamounts of 0.2-1.8% w/w.
 22. A method as claimed in claim 14 wherein thebulking agent is selected from the group consisting of calcium carbonateor talc and is present in amounts of up to 25% w/w.
 23. A method asclaimed in claim 14 wherein the lubricant is a fatty acid, preferablystearic acid.
 24. A method as claimed in claim 14 wherein the admixturefurther includes one or more of odour masking agents, antimicrobialagents, antifungal agents, wetting agents, colourants or dyes.
 25. Amethod as claimed in claim 1 wherein the admixture further includespolyethylene/ethyl vinyl acetate, blowing agent, dicumyl peroxide,stearic acid, zinc oxide and calcium carbonate.
 26. A method of treatingan environment to remove oil, chemical or hydrocarbon pollutantincluding: applying to said environment an adsorbent polymericcomposition which is oleophilic and capable of adsorption of chemicalsand hydrocarbons from land and water, the adsorbent compositionincluding polyethylene/vinyl acetate copolymer, catalyst, cross linkingagent, lubricant, blowing agent and bulking agent.
 27. A method asclaimed in claim 26 wherein said polyethylene/vinyl acetate copolymer isa polyethylene/ethyl vinyl acetate copolymer.
 28. A method as claimed inclaim 26 wherein said polyethylene/vinyl acetate copolymer is present inthe composition in an amount of 75-95% w/w.
 29. A method as claimed inclaim 26 wherein said polyethylene/vinyl acetate polymer is made up of2-30% w/w vinyl acetate.
 30. A method as claimed in claim 26 whereinsaid catalyst is selected from the group consisting of one or more ofzinc oxide, zinc stearate, lead, chromium, copper, cobalt, nickel,silica, compounds or ionic forms thereof and is present in amounts of0.2-2.0% w/w.
 31. A method as claimed in claim 26 wherein saidcrosslinking agent is selected from the group consisting of one or moreof diacyl peroxide, dialkyl peroxide, ketone peroxide, peroxydicarbonates, peroxy esters, tertiary alkyl hydroperoxides, tertiaryamyl peroxides, acid chlorides or hydrogen peroxides and is present inamounts of 0.2-1.8% w/w.
 32. A method as claimed in claim 26 wherein thebulking agent is selected from the group consisting of calcium carbonateor talc and is present in amounts of up to 25% w/w.
 33. A method asclaimed in claim 26 wherein the lubricant is a fatty acid, preferablystearic acid.
 34. A method as claimed in claim 26 wherein the adsorbentpolymeric composition further includes one or more of odour maskingagents, antimicrobial agents, antifungal agents, wetting agents,colourants or dyes.
 35. A method as claimed in claim 26 wherein theadsorbent polymeric composition further include polyethylene/ethyl vinylacetate, blowing agent, dicumyl peroxide, stearic acid, zinc oxide andcalcium carbonate.
 36. A filter for off site treatment of soil or watercontaminated by oil, chemicals or hydrocarbons, said filter including:an adsorbent polymeric composition which is oleophilic and capable ofadsorption of chemicals and hydrocarbons from land and water, theadsorbent composition including polyethylene/vinyl acetate copolymer,catalyst, cross linking agent, lubricant, blowing agent and bulkingagent.
 37. A filter as claimed in claim 36 wherein saidpolyethylene/vinyl acetate copolymer is a polyethylene/ethyl vinylacetate copolymer.
 38. A filter as claimed in claim 36 wherein saidpolyethylene/vinyl acetate copolymer is present in the composition in anamount of 75-95% w/w.
 39. A filter as claimed in claim 36 wherein saidpolyethylene/vinyl acetate polymer is made up of 2-30% w/w vinylacetate.
 40. A filter as claimed in claim 36 wherein said catalyst isselected from the group consisting of one or more of zinc oxide, zincstearate, lead, chromium, copper, cobalt, nickel, silica, compounds orionic forms thereof and is present in amounts of 0.2-2.0% w/w.
 41. Afilter as claimed in claim 36 wherein said crosslinking agent isselected from the group consisting of one or more of diacyl peroxide,dialkyl peroxide, ketone peroxide, peroxy dicarbonates, peroxy esters,tertiary alkyl hydroperoxides, tertiary amyl peroxides, acid chloridesor hydrogen peroxides and is present in amounts of 0.2-1.8% w/w.
 42. Afilter as claimed in claim 36 wherein the bulking agent is selected fromthe group consisting of calcium carbonate or talc and is present inamounts of up to 25% w/w.
 43. A filter as claimed in claim 36 whereinthe lubricant is a fatty acid, preferably stearic acid.
 44. A filter asclaimed in claim 36 wherein the adsorbent polymeric composition furtherincludes one or more of odour masking agents, antimicrobial agents,antifungal agents, wetting agents, colourants or dyes.
 45. A filter asclaimed in claim 36 wherein the adsorbent polymeric composition furtherincludes polyethylene/ethyl vinyl acetate, blowing agent, dicumylperoxide, stearic acid, zinc oxide and calcium carbonate.